CN109786720A - Preparation method and application method for aluminium chloride-carbon battery positive electrode - Google Patents

Preparation method and application method for aluminium chloride-carbon battery positive electrode Download PDF

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CN109786720A
CN109786720A CN201910104224.XA CN201910104224A CN109786720A CN 109786720 A CN109786720 A CN 109786720A CN 201910104224 A CN201910104224 A CN 201910104224A CN 109786720 A CN109786720 A CN 109786720A
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carbon
aluminium chloride
positive electrode
battery positive
suspension
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CN109786720B (en
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高炳亮
刘成员
李启明
刘智伟
牛宏坤
王兆文
胡宪伟
石忠宁
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Northeastern University China
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Northeastern University China
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
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  • Cell Electrode Carriers And Collectors (AREA)
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Abstract

Preparation method and application method for aluminium chloride-carbon battery positive electrode are placed in water ultrasonic cleaning the preparation method comprises the following steps: carbon cloth is placed in ultrasonic cleaning in ethyl alcohol by (1), in vacuum condition and 80~150 DEG C of dryings；(2) in organic solvent by carbon raw material dispersion, it is crushed by ultrasonication or high shear stirring and suspension is made；(3) pretreatment carbon cloth is immersed in suspension；Or suspension is added dropwise or is sprayed to pretreatment carbon cloth surface；Taking-up is placed in vacuum condition and 80~200 DEG C of dryings；Application method are as follows: be used as anode for aluminium chloride-carbon battery positive electrode using obtained, anode, cathode, diaphragm and electrolyte are assembled into aluminium chloride-carbon battery.Method preparation process of the invention is simple, low in cost, and product property is stablized, and can be mass-produced.

Description

Preparation method and application method for aluminium chloride-carbon battery positive electrode
Technical field
The invention belongs to aluminum cell technical field, in particular to a kind of system for aluminium chloride-carbon battery positive electrode Preparation Method and application method.
Background technique
Lithium ion battery realizes work because the advantages that its self discharge is small, specific discharge capacity is high has obtained practical application Industry metaplasia produces；But the natural abundance of elemental lithium is low, the defects of inflammable in air, easy formation dendrite, limits its further quotient Industry application；The negative electrode material of aluminium ion battery is metallic aluminium or alloy, and aluminium element is in nature rich reserves, and in air It is stabilized, specific discharge capacity density can reach 2980mAh/g, and volume and capacity ratio density is up to 8040mAh/cm3。
Up to the present aluminium ion battery is not commercialized also, lie substantially in the laboratory research stage； CN201510902386.X, which is disclosed, prepares graphene oxide using improved hummers method, then uses hydrazine hydrate reduction agent system Standby graphene anode material；CN201610390212.4 is disclosed deposits multilayer using chemical vapour deposition technique on foam metal Graphene prepares porous three-dimensional graphene anode material；CN201610845761.6 is disclosed graphene oxide or oxidation stone Black alkene inorganic salts mixed liquor prepares graphene oxide cloth and reduced graphene cloth positive electrode with electrospinning device； CN201610281036.0, which discloses for organic carbon source and graphite material to be added in solvent, carries out high pressure solvent thermal response and high temperature Carbonization prepares positive active material, then prepares positive electrode using coating process；CN201711173282.5 discloses chemical gas The foamy graphite powder and Kynoar of phase sedimentation preparation are dispersed in setting solvent, obtain foamy graphite slurry, Jiang Pao Foam graphite slurry is coated on substrate, after drying process, is formed foamy graphite carbon-coating on substrate and is coated with foam stone The substrate of black carbon-coating is immersed in the first setting solution, after substrate dissolution, is post-processed and is steeped to foamy graphite carbon-coating Foam graphite flake positive electrode；CN201710641041.2, which is disclosed, prepares graphene oxide foam using freeze-drying, then Electronation obtains grapheme foam, and high-temperature heat treatment is heat-treated to obtain ultra-high conducting grapheme foam positive electrode； CN201710685318.1 is disclosed expanded graphite after 2000~3000 DEG C of high-temperature process in the pressure of 1.5~35MPa Under be pressed into film as aluminium ion anode.
Currently, the preparation method of positive electrode with high performance is concentrated mainly on hummers method, chemical vapor deposition Method, electrostatic spinning technique prepare graphene cloth after graphene oxide cloth or reduction；These preparation methods complex process, cost compared with High, equipment requirement height, hinders the development of its commercialization.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method for aluminium chloride-carbon battery positive electrode and users The carbon material with graphite-structure after pulverization process is adsorbed on carbon cloth, just as aluminium ion battery by method Pole material while simplifying technique reduces cost, improves aluminum cell performance.
Preparation method for aluminium chloride-carbon battery positive electrode of the invention, sequentially includes the following steps:
1, carbon cloth is placed in progress 30~60min of ultrasonic cleaning in ethyl alcohol, is subsequently placed in deionized water and carries out 30~60min of ultrasonic cleaning, in the case where taking-up is placed on vacuum condition, 80~150 DEG C dry 12~for 24 hours, pre-processed Carbon cloth；
2, in organic solvent by carbon raw material dispersion, by ultrasonication or high shear stirring to the carbon in organic solvent Raw material is crushed and suspension is made；The carbon raw material is natural graphite, porous activated carbon, highly oriented graphite or graphitization Expanded graphite, purity 99.5~99.9%；The organic solvent is dehydrated alcohol, N-Methyl pyrrolidone, dimethyl formyl Amine, dimethyl acetamide or dimethyl sulfoxide；The mass ratio of carbon raw material and organic solvent is (1~10): 100；
3, pretreatment carbon cloth is immersed in suspension, is then taken out；Or suspension is added drop-wise to pretreatment carbon Fiber cloth surface；Or suspension is sprayed on pretreatment carbon cloth surface；Surface is covered with to the carbon fiber of suspension again Be arranged under vacuum condition, 80~200 DEG C dry 12~for 24 hours, be made for aluminium chloride-carbon battery positive electrode.
In above-mentioned step 2, the time of ultrasonication is 0.5~12h.
In above-mentioned step 2, the stirring rate of high shear stirring is 1000~2000rpm, 0.5~6h of time.
It is above-mentioned in aluminium chloride-carbon battery positive electrode, the density of the carbon material on carbon cloth surface is 0.5~ 10mg/cm2。
Application method for aluminium chloride-carbon battery positive electrode of the invention are as follows:
It is used as anode using for aluminium chloride-carbon battery positive electrode, using aluminium foil as cathode, using glass fibre Filter paper is assembled into aluminium chloride-carbon battery as diaphragm, by anode, cathode, diaphragm and electrolyte.
Above-mentioned aluminium chloride-carbon battery further includes collector and Soft Roll shell；The collector is carbon cloth, metal Molybdenum, tungsten or the metal foil for being attached with titanium nitride coating, wherein the material selection metallic nickel, stainless steel, metallic copper of metal foil, Metallic aluminium or Titanium.
Above-mentioned electrolyte is aluminium chloride -1- ethyl -3- methylimidazolium chloride, aluminium chloride -1- butyl -3- methyl chloride miaow Azoles, aluminium chloride-triethylamine hydrochloride, aluminium chloride-urea, aluminium chloride-acetamide, aluminium chloride-propionamide or aluminium chloride-butyryl Amine；AlCl in electrolyte3Molar percentage be 52~67%.
Additive is added in above-mentioned electrolyte, additive accounts for the 1~10% of electrolyte total mole number, and additive is LiCl, LiBr, NaCl, NaBr, EC (ethylene carbonate), THF (tetrahydrofuran) or DCE (1,2- dichloroethanes).
Compared with prior art, the advantages of method of the invention, is with beneficial effect:
1, preparation process is simply controllable, can be obtained by the mass ratio of control carbon material raw material and organic solvent, processing time Obtain the active material suspension of various concentration；The number for being added dropwise or being sprayed by control can obtain the positive material of different loads amount Material；
2, positive electrode is soap-free emulsion polymeization positive electrode, avoids electrolyte and binder reacts to destroy electrode knot Structure, and the three-dimensional porous reticular structure of carbon cloth substrate provides channel for the fast transferring of ion；
3, using the positive electrode as aluminium chloride-carbon battery of anode assembling, average working voltage is 1.5~2.0V, is put Electricity quality 100~350mAh/g of specific capacity, 200~650Wh/kg of mass-energy density metric density；
4, preparation process is simple, low in cost, and product property is stablized, and can be mass-produced.
Detailed description of the invention
Fig. 1 is the smashed Raman spectrogram of carbon raw material in the embodiment of the present invention 1；
Fig. 2 is the Flied emission scanning electron microscopy that aluminium chloride-carbon battery positive electrode is used in the embodiment of the present invention 1 Figure；
Fig. 3 is for aluminium chloride-carbon battery positive electrode in the embodiment of the present invention 1 in sweep speed 0.2mV/s condition Under cyclic voltammetry curve figure；
It for aluminium chloride-carbon battery positive electrode in current density is 100mA/g item that Fig. 4, which is in the embodiment of the present invention 1, Charging and discharging curve figure under part；In figure, ■ is charging, ● for electric discharge.
Specific embodiment
Ultrasonic power when carrying out ultrasonication in the embodiment of the present invention is 100~600W.
Vacuum condition in step 1 of the present invention and 3 is≤200Pa
The carbon cloth used in the embodiment of the present invention is commercial products.
The 12.5mg/cm of the carbon cloth used in the embodiment of the present invention2, with a thickness of 0.036cm；Using preceding by carbon fiber Cloth is cut into that (10~15) mm × (10~15) mm is rectangular or 10~18mm of diameter is round.
The carbon raw material used in the embodiment of the present invention is commercial products, purity 99.5~99.9%.
The anhydrous AlCl that electrolyte uses purity > 99% is prepared in the embodiment of the present invention3, it is placed directly in argon atmosphere It is saved backup in glove box.
LiCl, LiBr, NaCl, NaBr, EC (ethylene carbonate) for being used in the embodiment of the present invention, THF (tetrahydrofuran), DCE (1,2- dichloroethanes) is market analytical pure reagents, dry using initial vacuum and be placed in the glove box of argon atmosphere and protect It deposits spare.
EMIC, acetamide, urea, propionamide, the butyramide used in the embodiment of the present invention is commercially available reagent, before use It is dried in vacuo and is placed in the glove box of argon atmosphere and save backup.
Vacuum drying condition in the embodiment of the present invention are as follows: 60~120 DEG C of dryings 12~for 24 hours, vacuum degree≤50Pa.
Water and oxygen content are respectively less than 0.1ppm in the glove box used in the embodiment of the present invention.
The carbon cloth that uses in the embodiment of the present invention, metal molybdenum, tungsten and the metal foil of titanium nitride coating is attached with as city Product is purchased, preceding removing surface impurity is used.Purity is >=99.9%, and the preparation method of titanium carbide coating is as described in document (Adv.Sci.2018,5,1700712: earth element abundant prepares flexible current-collecting body for aluminium chloride-graphite cell).
Aluminium chloride-carbon battery in the embodiment of the present invention is under the conditions of current density is 100~1000mA/g, quality of discharging Specific capacity is 110~300mAh/g.
Embodiment 1
Carbon cloth is placed in progress ultrasonic cleaning 30min in ethyl alcohol, is subsequently placed in deionized water and carries out ultrasonic wave 30min is cleaned, in the case where taking-up is placed on vacuum condition, is dried at 80 DEG C for 24 hours, obtains pretreatment carbon cloth；
In organic solvent by carbon raw material dispersion, the carbon raw material in organic solvent is crushed simultaneously by ultrasonication Suspension is made；Carbon raw material is natural graphite；Organic solvent is N-Methyl pyrrolidone；The mass ratio of carbon raw material and organic solvent For 1:100；The Raman spectrum of the carbon raw material of acquisition is as shown in Figure 1；Wherein the time of ultrasonication is 0.5h；
Suspension is sprayed on pretreatment carbon cloth surface；The carbon cloth that surface is covered with suspension is placed in very again Under empty condition, dries for 24 hours, be made for aluminium chloride-carbon battery positive electrode at 80 DEG C；Flied emission scanning electron microscopy is such as Shown in Fig. 2；Above-mentioned is used in aluminium chloride-carbon battery positive electrode, and the density of the carbon material on carbon cloth surface is 0.5mg/cm2；Cyclic voltammetry, sweep speed 0.2mV/s, cyclic voltammetric song are carried out using Hai Chenhua electrochemical workstation Line chart is as shown in Figure 3；
Application method for aluminium chloride-carbon battery positive electrode are as follows:
It is used as anode using for aluminium chloride-carbon battery positive electrode, using aluminium foil as cathode, using glass fibre Filter paper is assembled into aluminium chloride-carbon battery as diaphragm, by anode, cathode, diaphragm and electrolyte；Aluminium chloride-carbon battery further includes Collector and Soft Roll shell；Collector is carbon cloth；Electrolyte is aluminium chloride -1- ethyl -3- methylimidazolium chloride；Electrolyte Middle AlCl3Molar percentage be 67%；
Constant current charge-discharge test is carried out using the new Weir battery test system in Shenzhen, aluminium chloride-carbon battery is close in electric current Degree is that the charging and discharging curve under the conditions of 100mA/g is as shown in Figure 4；Charge and discharge blanking voltage is 0.01~2.45V, the electric discharge of battery Specific discharge capacity 260mAh/g.
Embodiment 2
The preparation method is the same as that of Example 1, and difference is:
(1) carbon cloth is placed in progress ultrasonic cleaning 35min in ethyl alcohol, is subsequently placed in deionized water and carries out ultrasound Wave cleans 40min, in the case where taking-up is placed on vacuum condition, in 90 DEG C of dry 22h；
(2) in organic solvent by carbon raw material dispersion, powder is carried out to the carbon raw material in organic solvent by high shear stirring It is broken and suspension is made；Carbon raw material is porous activated carbon；Organic solvent is dehydrated alcohol；The mass ratio of carbon raw material and organic solvent For 2:100；The stirring rate of high shear stirring is 1000rpm, time 0.5h；
(3) pretreatment carbon cloth is immersed in suspension, is then taken out；Surface is covered with to the carbon fiber of suspension It is arranged under vacuum condition, in 100 DEG C of dry 20h；For in aluminium chloride-carbon battery positive electrode, carbon cloth surface The density of carbon material is 1mg/cm2；
With embodiment 1, difference is application method:
(1) collector used is metal molybdenum；
(2) electrolyte used is aluminium chloride -1- butyl -3- methylimidazolium chloride；AlCl in electrolyte3Mole percent Than being 66%；
(3) additive is added in electrolyte, additive accounts for the 1~10% of electrolyte total mole number, additive LiCl；
(4) current density of constant current charge-discharge test is 200mA/g, the electric discharge specific discharge capacity 200mAh/g of battery.
Embodiment 3
The preparation method is the same as that of Example 1, and difference is:
(1) carbon cloth is placed in progress ultrasonic cleaning 40min in ethyl alcohol, is subsequently placed in deionized water and carries out ultrasound Wave cleans 35min, in the case where taking-up is placed on vacuum condition, in 100 DEG C of dry 20h；
(2) carbon raw material is highly oriented graphite；Organic solvent is dimethylformamide；The mass ratio of carbon raw material and organic solvent For 3:100；The time of ultrasonication is 2h；
(3) suspension is added drop-wise to pretreatment carbon cloth surface；The carbon cloth that surface is covered with suspension is placed in Under vacuum condition, in 120 DEG C of dry 18h；For in aluminium chloride-carbon battery positive electrode, the carbon material on carbon cloth surface Density be 3mg/cm2；
With embodiment 1, difference is application method:
(1) collector used is tungsten；
(2) electrolyte used is aluminium chloride-triethylamine hydrochloride；AlCl in electrolyte3Molar percentage be 64%；
(3) additive is added in electrolyte, additive accounts for the 1~10% of electrolyte total mole number, additive LiBr；
(4) current density of constant current charge-discharge test is 200mA/g, the electric discharge specific discharge capacity 180mAh/g of battery.
Embodiment 4
The preparation method is the same as that of Example 1, and difference is:
(1) carbon cloth is placed in progress ultrasonic cleaning 45min in ethyl alcohol, is subsequently placed in deionized water and carries out ultrasound Wave cleans 35min, in the case where taking-up is placed on vacuum condition, in 110 DEG C of dry 18h；
(2) in organic solvent by carbon raw material dispersion, powder is carried out to the carbon raw material in organic solvent by high shear stirring It is broken and suspension is made；Carbon raw material is graphitization expansion graphite；Organic solvent is dimethyl acetamide；Carbon raw material and organic solvent Mass ratio be 4:100；The stirring rate of high shear stirring is 1500rpm, time 1h；
(3) pretreatment carbon cloth is immersed in suspension, is then taken out；Surface is covered with to the carbon fiber of suspension It is arranged under vacuum condition, in 140 DEG C of dry 16h；For in aluminium chloride-carbon battery positive electrode, carbon cloth surface The density of carbon material is 4mg/cm2；
With embodiment 1, difference is application method:
(1) collector used is the metal foil for being attached with titanium nitride coating, the wherein material selection metallic nickel of metal foil；
(2) electrolyte used is aluminium chloride-urea；AlCl in electrolyte3Molar percentage be 62%；
(3) additive is added in electrolyte, additive accounts for the 1~10% of electrolyte total mole number, additive NaCl；
(4) current density of constant current charge-discharge test is 100mA/g, the electric discharge specific discharge capacity 120mAh/g of battery.
Embodiment 5
The preparation method is the same as that of Example 1, and difference is:
(1) carbon cloth is placed in progress ultrasonic cleaning 50min in ethyl alcohol, is subsequently placed in deionized water and carries out ultrasound Wave cleans 60min, in the case where taking-up is placed on vacuum condition, in 120 DEG C of dry 16h；
(2) carbon raw material is porous activated carbon；Organic solvent is dimethyl sulfoxide；The mass ratio of carbon raw material and organic solvent is 6:100；The time of ultrasonication is 5h；
(3) suspension is added drop-wise to pretreatment carbon cloth surface；The carbon cloth that surface is covered with suspension is placed in Under vacuum condition, in 150 DEG C of dry 15h；For in aluminium chloride-carbon battery positive electrode, the carbon material on carbon cloth surface Density be 5mg/cm2；
With embodiment 1, difference is application method:
(1) collector used for the metal foil for being attached with titanium nitride coating, wherein metal foil material selection become rusty steel；
(2) electrolyte used is aluminium chloride-acetamide；AlCl in electrolyte3Molar percentage be 60%；
(3) additive is added in electrolyte, additive accounts for the 1~10% of electrolyte total mole number, additive NaBr；
(4) current density of constant current charge-discharge test is 150mA/g, the electric discharge specific discharge capacity 150mAh/g of battery.
Embodiment 6
The preparation method is the same as that of Example 1, and difference is:
(1) carbon cloth is placed in progress ultrasonic cleaning 55min in ethyl alcohol, is subsequently placed in deionized water and carries out ultrasound Wave cleans 50min, in the case where taking-up is placed on vacuum condition, in 130 DEG C of dry 15h；
(2) in organic solvent by carbon raw material dispersion, powder is carried out to the carbon raw material in organic solvent by high shear stirring It is broken and suspension is made；Carbon raw material is highly oriented graphite；Organic solvent is dimethyl acetamide；The matter of carbon raw material and organic solvent Amount is than being 8:100；The stirring rate of high shear stirring is 1800rpm, time 4h；
(3) carbon cloth that surface is covered with suspension is placed under vacuum condition, in 160 DEG C of dry 14h；For chlorination In aluminium-carbon battery positive electrode, the density of the carbon material on carbon cloth surface is 6mg/cm2；
With embodiment 1, difference is application method:
(1) collector used is the metal foil for being attached with titanium nitride coating, the wherein material selection metallic copper of metal foil；
(2) electrolyte used is aluminium chloride-propionamide；AlCl in electrolyte3Molar percentage be 57%；
(3) additive is added in electrolyte, additive accounts for the 1~10% of electrolyte total mole number, additive EC；
(4) current density of constant current charge-discharge test is 100mA/g, the electric discharge specific discharge capacity 170mAh/g of battery.
Embodiment 7
The preparation method is the same as that of Example 1, and difference is:
(1) carbon cloth is placed in progress ultrasonic cleaning 60min in ethyl alcohol, is subsequently placed in deionized water and carries out ultrasound Wave cleans 30min, in the case where taking-up is placed on vacuum condition, in 140 DEG C of dry 14h；
(2) carbon raw material is graphitization expansion graphite；Organic solvent is dehydrated alcohol；The mass ratio of carbon raw material and organic solvent For 9:100；The time of ultrasonication is 12h；
(3) pretreatment carbon cloth is immersed in suspension, is then taken out；Surface is covered with to the carbon fiber of suspension It is arranged under vacuum condition, in 180 DEG C of dry 13h；For in aluminium chloride-carbon battery positive electrode, carbon cloth surface The density of carbon material is 8mg/cm2；
With embodiment 1, difference is application method:
(1) collector used is the metal foil for being attached with titanium nitride coating, the wherein material selection metallic aluminium of metal foil；
(2) electrolyte used is aluminium chloride-butyramide；AlCl in electrolyte3Molar percentage be 54%；
(3) additive is added in electrolyte, additive accounts for the 1~10% of electrolyte total mole number, additive THF；
(4) current density of constant current charge-discharge test is 500mA/g, the electric discharge specific discharge capacity 150mAh/g of battery.
Embodiment 8
The preparation method is the same as that of Example 1, and difference is:
(1) carbon cloth is placed in progress ultrasonic cleaning 45min in ethyl alcohol, is subsequently placed in deionized water and carries out ultrasound Wave cleans 45min, in the case where taking-up is placed on vacuum condition, in 150 DEG C of dry 12h；
(2) in organic solvent by carbon raw material dispersion, powder is carried out to the carbon raw material in organic solvent by high shear stirring It is broken and suspension is made；Carbon raw material is graphitization expansion graphite；Organic solvent is dimethylformamide；Carbon raw material and organic solvent Mass ratio be 10:100；The stirring rate of high shear stirring is 2000rpm, time 6h；
(3) suspension is added drop-wise to pretreatment carbon cloth surface；The carbon cloth that surface is covered with suspension is placed in Under vacuum condition, in 200 DEG C of dry 12h；For in aluminium chloride-carbon battery positive electrode, the carbon material on carbon cloth surface Density be 10mg/cm2；
With embodiment 1, difference is application method:
(1) collector used is the metal foil for being attached with titanium nitride coating, the wherein material selection gold metal of metal foil Titanium；
(2) electrolyte used is aluminium chloride-butyramide；AlCl in electrolyte3Molar percentage be 52%；
(3) additive is added in electrolyte, additive accounts for the 1~10% of electrolyte total mole number, additive DCE；
(4) current density of constant current charge-discharge test is 1000mA/g, the electric discharge specific discharge capacity 110mAh/g of battery.

Claims (8)

1. a kind of preparation method for aluminium chloride-carbon battery positive electrode, it is characterised in that sequentially include the following steps:
(1) carbon cloth is placed in progress 30~60min of ultrasonic cleaning in ethyl alcohol, is subsequently placed in deionized water and carries out ultrasound Wave cleans 30~60min, in the case where taking-up is placed on vacuum condition, 80~150 DEG C dry 12~for 24 hours, obtain pretreatment carbon fiber Wei Bu；
(2) in organic solvent by carbon raw material dispersion, former to the carbon in organic solvent by ultrasonication or high shear stirring Material is crushed and suspension is made；The carbon raw material is that natural graphite, porous activated carbon, highly oriented graphite or graphitization are swollen Swollen graphite, purity 99.5~99.9%；The organic solvent be dehydrated alcohol, N-Methyl pyrrolidone, dimethylformamide, Dimethyl acetamide or dimethyl sulfoxide；The mass ratio of carbon raw material and organic solvent is (1~10): 100；
(3) pretreatment carbon cloth is immersed in suspension, is then taken out；Or suspension is added drop-wise to pretreatment carbon fiber Cloth surface；Or suspension is sprayed on pretreatment carbon cloth surface；The carbon fiber that surface is covered with suspension is arranged again Under vacuum condition, 80~200 DEG C dry 12~for 24 hours, be made for aluminium chloride-carbon battery positive electrode.
2. the preparation method according to claim 1 for aluminium chloride-carbon battery positive electrode, it is characterised in that step (2) in, the time of ultrasonication is 0.5~12h.
3. the preparation method according to claim 1 for aluminium chloride-carbon battery positive electrode, it is characterised in that step (2) in, the stirring rate of high shear stirring is 1000~2000rpm, 0.5~6h of time.
4. the preparation method according to claim 1 for aluminium chloride-carbon battery positive electrode, it is characterised in that described For in aluminium chloride-carbon battery positive electrode, the density of the carbon material on carbon cloth surface to be 0.5~10mg/cm2。
5. a kind of application method for aluminium chloride-carbon battery positive electrode, it is characterised in that using described in claim 1 Method preparation is used as anode for aluminium chloride-carbon battery positive electrode, using aluminium foil as cathode, is filtered using glass fibre Paper is assembled into aluminium chloride-carbon battery as diaphragm, by anode, cathode, diaphragm and electrolyte.
6. the application method according to claim 5 for aluminium chloride-carbon battery positive electrode, it is characterised in that described Aluminium chloride-carbon battery further include collector and Soft Roll shell；The collector be carbon cloth, metal molybdenum, tungsten or It is attached with the metal foil of titanium nitride coating, wherein material selection metallic nickel, stainless steel, metallic copper, metallic aluminium or the gold of metal foil Belong to titanium.
7. the application method according to claim 5 for aluminium chloride-carbon battery positive electrode, it is characterised in that described Electrolyte be aluminium chloride -1- ethyl -3- methylimidazolium chloride, aluminium chloride -1- butyl -3- methylimidazolium chloride, aluminium chloride-three Ethylamine hydrochloride, aluminium chloride-urea, aluminium chloride-acetamide, aluminium chloride-propionamide or aluminium chloride-butyramide；In electrolyte AlCl3Molar percentage be 52~67%.
8. the application method according to claim 5 for aluminium chloride-carbon battery positive electrode, it is characterised in that described Electrolyte in be added with additive, additive accounts for the 1~10% of electrolyte total mole number, additive LiCl, LiBr, NaCl, NaBr, EC, THF or DCE.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110350147A (en) * 2019-06-06 2019-10-18 西安交通大学 A kind of integrated-type tunica fibrosa battery component
WO2020155565A1 (en) * 2019-02-01 2020-08-06 东北大学 Preparation method and use method for positive electrode material of aluminum chloride-carbon battery
CN114141992A (en) * 2021-11-30 2022-03-04 四川启睿克科技有限公司 Self-propagating alloyed lithium negative electrode and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04355051A (en) * 1991-05-31 1992-12-09 Oowada Carbon Kogyo Kk Separator for fuel cell
CN106340683A (en) * 2016-09-06 2017-01-18 北京理工大学 Aluminum metal-based bearing and energy storage all-in-one system
CN107369846A (en) * 2017-07-14 2017-11-21 北京理工大学 Electrode slice and preparation method thereof and aluminium ion battery
CN108140881A (en) * 2015-12-15 2018-06-08 里兰斯坦福初级大学理事会 For improved electrolyte, current-collector and the adhesive of chargeable metal ion battery
CN108615933A (en) * 2018-05-16 2018-10-02 东莞市振华新能源科技有限公司 A kind of aluminium ion battery and preparation method thereof based on novel anode material
CN108899482A (en) * 2018-05-29 2018-11-27 绿业中试低碳科技（镇江）有限公司 Aluminium ion battery and its positive electrode

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109786720B (en) * 2019-02-01 2021-03-16 东北大学 Preparation method and use method of positive electrode material for aluminum chloride-carbon battery

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04355051A (en) * 1991-05-31 1992-12-09 Oowada Carbon Kogyo Kk Separator for fuel cell
CN108140881A (en) * 2015-12-15 2018-06-08 里兰斯坦福初级大学理事会 For improved electrolyte, current-collector and the adhesive of chargeable metal ion battery
CN106340683A (en) * 2016-09-06 2017-01-18 北京理工大学 Aluminum metal-based bearing and energy storage all-in-one system
CN107369846A (en) * 2017-07-14 2017-11-21 北京理工大学 Electrode slice and preparation method thereof and aluminium ion battery
CN108615933A (en) * 2018-05-16 2018-10-02 东莞市振华新能源科技有限公司 A kind of aluminium ion battery and preparation method thereof based on novel anode material
CN108899482A (en) * 2018-05-29 2018-11-27 绿业中试低碳科技（镇江）有限公司 Aluminium ion battery and its positive electrode

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020155565A1 (en) * 2019-02-01 2020-08-06 东北大学 Preparation method and use method for positive electrode material of aluminum chloride-carbon battery
CN110350147A (en) * 2019-06-06 2019-10-18 西安交通大学 A kind of integrated-type tunica fibrosa battery component
CN114141992A (en) * 2021-11-30 2022-03-04 四川启睿克科技有限公司 Self-propagating alloyed lithium negative electrode and preparation method thereof

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